High-strength tungsten wire substrate diamond wire and preparation method thereof

Abstract

The application relates to the technical field of metal powder processing preparation of tungsten wire diamond wire, and discloses a high-strength tungsten wire base material diamond wire and a preparation method thereof, which comprises the following steps: uniformly mixing tungsten powder and modified materials, then adding cobalt hydride powder, lanthanum oxide powder, molybdenum powder and niobium powder, vacuum drying, ball milling, and obtaining a composite powder; the composite powder is compressed and sintered to obtain a sintered blank, the sintered blank is opened and drawn to obtain a tungsten wire base material; the tungsten wire base material is plated with nickel for the first time, plated with sand for the second time, plated with nickel for the third time, then washed with water and heat treated to obtain the tungsten wire base material diamond wire. The tungsten powder is used as the base material, the modified materials, the cobalt hydride powder, the lanthanum oxide powder, the molybdenum powder and the niobium powder are added, a high-performance sintered blank is prepared through a powder metallurgy method, the sintered blank is forged and drawn to prepare the tungsten wire base material, and the tungsten wire base material diamond wire prepared through the first-time nickel plating, the second-time sand plating and the third-time nickel plating has high mechanical strength.

Description

Technical Field

[0001] This invention relates to the field of metal powder processing for preparing tungsten-diamond wire, specifically to a high-strength tungsten-based diamond wire and its preparation method. Background Technology

[0002] Diamond wire is short for diamond cutting wire. Its tungsten wire substrate diamond wire is made by uniformly solidifying diamond particles on the tungsten wire substrate. It belongs to the linear cutting tools of superhard materials and has the cutting ability of high temperature resistance, corrosion resistance, high strength, low wire breakage rate and high precision. It is the foundation for ensuring the stable, reliable and efficient operation of cutting equipment.

[0003] Tungsten wire substrates consist of tungsten powder, rare earth oxides (rhenium oxide, lanthanum oxide), and solid solution strengthening phases (rhenium, molybdenum, hafnium, niobium, iron, cobalt). High-performance sintered blanks are mainly prepared by powder metallurgy, followed by forging and drawing processes to obtain tungsten wire substrates, which have high mechanical strength. During the wire drawing process, the tungsten wire substrate needs to withstand huge friction and compressive forces, which can easily lead to wire breakage. In addition, the tungsten wire substrate is prone to poor interfacial bonding, forming pores or cracks, which affects the mechanical strength of the diamond wire in the tungsten wire substrate. Summary of the Invention

[0004] This invention provides a high-strength tungsten wire substrate diamond wire and its preparation method, which solves the problems of wire breakage and poor interfacial bonding in tungsten wire substrates during wire drawing.

[0005] The technical solution of this invention: A method for preparing high-strength tungsten wire substrate diamond wire includes the following steps: S1. Mix tungsten powder with the modified material evenly, then add cobalt hydride powder, lanthanum oxide powder, molybdenum powder, and niobium powder. After vacuum drying and ball milling, a composite powder is obtained. S2. The composite powder is pressed and sintered to obtain a sintered green body. The sintered green body is then cut and drawn to obtain a tungsten wire substrate. S3. After the tungsten wire substrate undergoes a first nickel plating, a second sand plating, and a third nickel plating, it is then washed with water and heat-treated to obtain tungsten wire substrate diamond wire. The modified material is obtained by mixing and reacting modified titanium carbide nanosheets with zinc powder, and then mixing them with sodium carboxymethyl cellulose. The modified titanium carbide nanosheets are obtained by synthesizing nano-zirconium dioxide on the surface of titanium carbide nanosheets and then coating them with a silicon dioxide nanolayer.

[0006] Further, in step S1, the mass ratio of tungsten powder, modified material, cobalt hydride powder, lanthanum oxide powder, molybdenum powder, and niobium powder is 100:(2-3):(1-1.5):(1-1.2):(3-4):(2-3).

[0007] Furthermore, in step S1, the vacuum drying temperature is 100-110℃, the vacuum degree is 4-6Pa, and the vacuum drying time is 15-20min.

[0008] Further, in step S1, the ball milling is carried out in a ball mill, the ball material is silicon carbide ceramic grinding balls with a diameter of 10 mm, the ball-to-material ratio in the ball mill is (8-10):1, the rotation speed is 200-300 r / min, and the ball milling time is 10-15 h.

[0009] Furthermore, in step S2, the pressing pressure is 300-350 MPa, and the pressing time is 1-2 min.

[0010] Furthermore, in step S2, the sintering temperature is 1500-1600℃ and the sintering time is 2-4h.

[0011] Furthermore, in step S2, the diameter of the tungsten wire substrate is 55-60 μm.

[0012] Furthermore, in step S2, the billet temperature is 1350-1450℃, the deformation per pass is 15-25%, and the billet holding time is 10-20 min.

[0013] Furthermore, in step S2, the drawing temperature is 900-1000℃, and the holding time is 10-20 minutes.

[0014] Furthermore, in step S3, the first nickel plating: the plating solution is a nickel sulfate solution with a concentration of 5-10 g / L, and the thickness of the first plating layer is 1.5-2 μm.

[0015] Further, in step S3, the second sand plating: the plating solution is a nickel sulfamate plating solution containing 10-15 g / L of diamond particles, the particle size of the diamond particles is 50-80 nm, and the thickness of the second plating layer is 0.5-1 μm.

[0016] Furthermore, in step S3, the third nickel plating: the plating solution is a nickel sulfate solution with a concentration of 5-10 g / L, and the thickness of the third plating layer is 1.8-2.2 μm.

[0017] Further, in step S3, the water washing specifically involves ultrasonic cleaning at 40-60 kHz and 50-60 °C for 10-20 minutes.

[0018] Furthermore, in step S3, the heat treatment temperature is 450-500℃ and the heat treatment time is 20-30min.

[0019] Furthermore, the modified material is specifically prepared by the following steps: A1. Add zirconium oxychloride octahydrate and titanium carbide nanosheets to deionized water, stir evenly, add ammonia, glycine and potassium chloride, stir, place in a reaction vessel, carry out hydrothermal reaction at 170-190℃ for 20-22h, cool to room temperature, filter, wash and dry to obtain titanium carbide nanosheets coated with nano-zirconia. A2. Titanium carbide nanosheets coated with nano-zirconia were mixed with deionized water and ethanol, ultrasonically dispersed, and then sodium hydroxide solution was added to adjust the pH. Tetraethyl orthosilicate was then added, and the mixture was stirred and reacted. After filtration, washing, and drying, modified titanium carbide nanosheets were obtained. A3. Mix the modified titanium carbide nanosheets and zinc powder, stir evenly, and after the adsorption is complete, place them in a reaction furnace and calcine at 1000-1100℃ for 2-4 hours. Cool to room temperature, wash and dry to obtain composite titanium carbide nanosheets. A4. Add sodium carboxymethyl cellulose to deionized water, stir evenly, add composite titanium carbide nanosheets, stir at 40-50℃ for 10-15 min, let stand, filter, wash, and dry to obtain the modified material.

[0020] Furthermore, during the A1 reaction described above, the surface of the titanium carbide nanosheets contains a large number of hydroxyl groups, which can adsorb zirconium ions from zirconium oxychloride octahydrate onto the surface of the titanium carbide nanosheets. Ammonia water acts as a precipitant, which can react with zirconium ions to form zirconium hydroxide precipitate. After hydrothermal reaction, the zirconium hydroxide precipitate decomposes to form zirconium oxide crystals. Glycine and potassium chloride can regulate the crystal phase of zirconium dioxide, thereby forming nano-zirconia on the surface of the titanium carbide nanosheets, resulting in titanium carbide nanosheets coated with nano-zirconia.

[0021] Furthermore, during the A2 reaction described above, under alkaline conditions, the hydroxyl groups generated by the hydrolysis of tetraethyl orthosilicate can chemically bond with the hydroxyl groups on the surface of titanium carbide nanosheets coated with nano-zirconia. As the hydrolysis and condensation reaction proceeds, the silica layer generated by the hydrolysis of tetraethyl orthosilicate is coated onto the surface of the titanium carbide nanosheets coated with nano-zirconia, thereby forming a silica layer with a thickness of 18-20 nm on the surface of the titanium carbide nanosheets. This forms a layered structure with the titanium carbide nanosheets, and the formed silica layer has a porous structure, resulting in modified titanium carbide nanosheets.

[0022] Furthermore, during the A3 reaction process described above, the silica layer on the surface of the modified titanium carbide nanosheets has a porous structure and good adsorption properties, enabling it to adsorb zinc powder onto the surface of the modified titanium carbide nanosheets. Upon calcination at high temperature, the zinc powder is oxidized to generate zinc oxide vapor, which is then adsorbed onto the surface of the modified titanium carbide nanosheets to form zinc oxide crystal nuclei. As the reaction proceeds, the zinc oxide crystal nuclei grow directionally to form four-needle-shaped zinc oxide whiskers, thus achieving the formation of four-needle-shaped zinc oxide whiskers on the surface of the modified titanium carbide nanosheets and obtaining composite titanium carbide nanosheets.

[0023] Furthermore, in the A4 reaction process described above, sodium carboxymethyl cellulose contains a large number of carboxyl groups, which have good adhesion and can coat the surface of composite titanium carbide nanosheets to obtain modified materials.

[0024] Further, in step A1, the mass ratio of zirconium oxychloride octahydrate, titanium carbide nanosheets, deionized water, ammonia, glycine, and potassium chloride is (1-1.5):(1.5-2):(100-120):(1.5-2):(0.3-0.5):(0.7-0.9).

[0025] Further, in step A2, the mass ratio of the titanium carbide nanosheets coated with nano-zirconia, deionized water, ethanol and tetraethyl orthosilicate is (2-2.3):(45-55):(40-45):(1.8-2).

[0026] Further, in step A3, the mass ratio of the modified titanium carbide nanosheets to zinc powder is (2.5-3):(2-2.3).

[0027] Further, in step A4, the mass ratio of sodium carboxymethyl cellulose, deionized water, and composite titanium carbide nanosheets is (0.1-0.2):(80-100):(2-2.3).

[0028] The present invention has the following beneficial effects: (1) In the technical solution of the present invention, nano-zirconia is formed on the surface of titanium carbide nanosheets. On the one hand, the synthesized nano-zirconia, as a wear-resistant aggregate, can improve the wear resistance of tungsten wire substrate and avoid the tungsten wire substrate having to withstand huge friction and compression forces during the wire drawing process, which can easily lead to wire breakage and reduce the strength of the diamond wire of tungsten wire substrate. On the other hand, titanium carbide nanosheets, as a carrier of nano-zirconia, can prevent nano-zirconia from agglomerating. Moreover, the layered structure of titanium carbide nanosheets, as a physical barrier to the movement of dislocations in tungsten wire substrate, hinders the dislocation slip of tungsten wire substrate and improves the mechanical strength of tungsten alloy.

[0029] (2) In the technical solution of the present invention, a silicon dioxide layer is formed on the surface of titanium carbide nanosheets to form a layered structure with the titanium carbide nanosheets. On the one hand, during the wire drawing process, the layered structure formed can absorb and weaken the stress generated by the wire drawing, avoid the wire drawing stress being too large, which would cause the tungsten wire substrate to break, and improve the strength of the diamond wire of the tungsten wire substrate. On the other hand, as an intermediate layer, nano-zirconia can slide between the titanium carbide nanosheets and the silicon dioxide layer during the wire drawing process, play the role of a rolling bearing, improve the tensile properties of the tungsten wire substrate, and thus provide diamond wire with higher strength.

[0030] (3) In the technical solution of the present invention, four needle-shaped zinc oxide whiskers are formed on the surface of modified titanium carbide nanosheets. The four needle-shaped zinc oxide whiskers improve the surface roughness of modified titanium carbide nanosheets and improve the dispersion of modified titanium carbide nanosheets in tungsten wire substrate raw materials, thereby forming a denser tungsten wire substrate. The formed four needle-shaped zinc oxide whiskers have a unique four-dimensional spatial structure. Four needle-shaped crystals extend radially from the core, which can form a mechanical interlock with the tungsten wire substrate, thereby fixing the modified titanium carbide nanosheets in the tungsten wire substrate system and preventing the titanium carbide nanosheets from slipping on the tungsten wire substrate. This prevents the titanium carbide nanosheets from playing the role of rolling bearings during the wire drawing process, thereby enhancing the tensile strength of the tungsten wire substrate. In addition, the four needle-shaped zinc oxide whiskers have a large gripping force with the substrate, which can effectively transfer the load and enhance the mechanical strength of the diamond wire in the tungsten wire substrate.

[0031] (4) In the technical solution of the present invention, sodium carboxymethyl cellulose is coated on the surface of composite titanium carbide nanosheets to form a modified material. On the one hand, the carboxyl groups contained in sodium carboxymethyl cellulose can be adsorbed on the surface of tungsten powder, so that the modified material is coated on the surface of tungsten powder, which improves the surface roughness of tungsten powder, increases the contact area between tungsten powder and other metal elements, which is conducive to the synthesis of more dense tungsten wire substrate diamond wire, and improves the mechanical strength of tungsten wire substrate diamond wire. In addition, during the sintering process, the carbon elements formed by the carbonization of carboxymethyl cellulose can react with the metal elements in the raw materials of tungsten wire substrate to form a carbide reinforcing phase, which is dispersed in the tungsten wire substrate, thereby improving the mechanical properties of tungsten wire substrate diamond wire.

[0032] (5) In the technical solution of the present invention, tungsten powder is used as the base material, and modified materials, cobalt hydride powder, lanthanum oxide powder, molybdenum powder and niobium powder are added. A high-performance sintered billet is prepared by powder metallurgy. The sintered billet is forged and drawn to prepare tungsten wire substrate. The tungsten wire substrate diamond wire prepared by the first nickel plating, the second sand plating and the third nickel plating has high mechanical strength. The tungsten wire substrate is not prone to wire breakage during the wire drawing process and the tungsten wire substrate interface has good bonding. Detailed Implementation

[0033] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0034] The raw materials used in the embodiments of this invention are shown below, and all reagents used are analytical grade.

[0035] The average particle size of tungsten powder, cobalt hydride powder, lanthanum oxide powder, molybdenum powder, and niobium powder is 4.5 μm.

[0036] The cobalt hydride powder has a particle size of 1.5 μm.

[0037] The titanium carbide nanosheets had a diameter of 5 μm and were purchased from Zhongke Jinyan (Beijing) Technology Co., Ltd.

[0038] The zinc powder has a particle size of 30 nm.

[0039] Example 1 A method for preparing high-strength tungsten wire substrate diamond wire includes the following steps: S1. Tungsten powder and modified materials are mixed evenly, then cobalt hydride powder, lanthanum oxide powder, molybdenum powder, and niobium powder are added. After vacuum drying and ball milling, a composite powder is obtained. The mass ratio of tungsten powder, modified materials, cobalt hydride powder, lanthanum oxide powder, molybdenum powder, and niobium powder is 100:2:1:1:3:2. The vacuum drying temperature is 100℃, the vacuum degree is 4Pa, and the vacuum drying time is 15min. Ball milling is carried out in a ball mill, using silicon carbide ceramic grinding balls with a diameter of 10mm. The ball-to-material ratio in the ball mill is 8:1, the rotation speed is 200r / min, and the ball milling time is 10h. S2. The composite powder is pressed and sintered to obtain a sintered green body. The sintered green body is then roughened and drawn to obtain a tungsten wire substrate. The pressing pressure is 300 MPa, the pressing time is 1 min, the sintering temperature is 1500℃, the sintering time is 2 h, the diameter of the tungsten wire substrate is 58 μm, the roughing temperature is 1350℃, the deformation per pass is 15%, the roughing holding time is 10 min, and the drawing temperature is 900℃, the holding time is 10 min. S3. Tungsten wire substrate undergoes a first nickel plating, a second sand plating, and a third nickel plating, followed by water washing and heat treatment to obtain tungsten wire substrate diamond wire. Specifically, the first nickel plating uses a 5 g / L nickel sulfate solution, resulting in a first coating thickness of 1.5 μm; the second sand plating uses a nickel sulfamate plating solution containing 10 g / L diamond particles with a particle size of 50 nm, resulting in a second coating thickness of 0.5 μm; the third nickel plating uses a 5 g / L nickel sulfate solution, resulting in a third coating thickness of 1.8 μm; the water washing process involves ultrasonic cleaning at 40 kHz and 50 °C for 10 min; and the heat treatment temperature is 450 °C for 20 min.

[0040] The modified material is prepared by the following steps: A1. Zirconium oxychloride octahydrate and titanium carbide nanosheets were added to deionized water and stirred until homogeneous. Ammonia, glycine, and potassium chloride were added, and the mixture was stirred at 85°C for 10 min. The mixture was then placed in a reaction vessel and subjected to a hydrothermal reaction at 170°C for 20 h. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 80°C for 3 h to obtain titanium carbide nanosheets coated with nano-zirconium dioxide. The mass ratio of zirconium oxychloride octahydrate, titanium carbide nanosheets, deionized water, ammonia, glycine, and potassium chloride was 1:1.5:100:1.5:0.3:0.7. A2. Titanium carbide nanosheets coated with nano-zirconia were mixed with deionized water and ethanol, and ultrasonically dispersed at 40 kHz for 20 min. The pH was adjusted to 9 by adding 1 mol / L sodium hydroxide solution, and tetraethyl orthosilicate was added. The mixture was stirred and reacted at 40 °C for 6 h. After filtration, the mixture was washed three times with deionized water and dried in an oven at 60 °C for 10 min to obtain modified titanium carbide nanosheets. The mass ratio of titanium carbide nanosheets coated with nano-zirconia, deionized water, ethanol and tetraethyl orthosilicate was 2:45:40:1.8. A3. Modified titanium carbide nanosheets and zinc powder were mixed and stirred at 100 r / min for 1 h. After adsorption was complete, the mixture was placed in a reactor and calcined at 1000℃ for 2 h. After cooling to room temperature, the mixture was washed three times with deionized water and dried in an oven at 70℃ for 10 min to obtain composite titanium carbide nanosheets. The mass ratio of modified titanium carbide nanosheets to zinc powder was 2.5:2. A4. Add sodium carboxymethyl cellulose to deionized water, stir evenly, add composite titanium carbide nanosheets, stir at 40℃ for 10 min, let stand for 1 h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10 min to obtain the modified material; the mass ratio of sodium carboxymethyl cellulose, deionized water and composite titanium carbide nanosheets is 0.1:80:2.

[0041] Example 2 A method for preparing high-strength tungsten wire substrate diamond wire includes the following steps: S1. Tungsten powder and modified materials are mixed evenly, then cobalt hydride powder, lanthanum oxide powder, molybdenum powder, and niobium powder are added. After vacuum drying and ball milling, a composite powder is obtained. The mass ratio of tungsten powder, modified materials, cobalt hydride powder, lanthanum oxide powder, molybdenum powder, and niobium powder is 100:2.5:1.3:1.1:3.5:2.5. The vacuum drying temperature is 105℃, the vacuum degree is 5Pa, and the vacuum drying time is 18min. Ball milling is carried out in a ball mill, using silicon carbide ceramic grinding balls with a diameter of 10mm. The ball-to-material ratio in the ball mill is 9:1, the rotation speed is 250r / min, and the ball milling time is 13h. S2. The composite powder is pressed and sintered to obtain a sintered green body. The sintered green body is then roughened and drawn to obtain a tungsten wire substrate. The pressing pressure is 330 MPa, the pressing time is 1.5 min, the sintering temperature is 1550℃, the sintering time is 3 h, the diameter of the tungsten wire substrate is 60 μm, the roughing temperature is 1400℃, the deformation per pass is 20%, the roughing holding time is 15 min, and the drawing temperature is 950℃, the holding time is 15 min. S3. Tungsten wire substrate undergoes a first nickel plating, a second sand plating, and a third nickel plating, followed by water washing and heat treatment to obtain tungsten wire substrate diamond wire. Specifically, the first nickel plating uses an 8 g / L nickel sulfate solution, resulting in a first coating thickness of 1.8 μm; the second sand plating uses a nickel sulfamate plating solution containing 13 g / L diamond particles with a particle size of 70 nm, resulting in a second coating thickness of 0.8 μm; the third nickel plating uses an 8 g / L nickel sulfate solution, resulting in a third coating thickness of 2 μm; the water washing process involves ultrasonic cleaning at 50 kHz and 55 °C for 15 min; and the heat treatment temperature is 480 °C for 25 min.

[0042] The modified material is prepared by the following steps: A1. Zirconium oxychloride octahydrate and titanium carbide nanosheets were added to deionized water and stirred until homogeneous. Ammonia, glycine, and potassium chloride were added, and the mixture was stirred at 85°C for 10 min. The mixture was then placed in a reaction vessel and subjected to a hydrothermal reaction at 180°C for 21 h. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 80°C for 3 h to obtain titanium carbide nanosheets coated with nano-zirconium dioxide. The mass ratio of zirconium oxychloride octahydrate, titanium carbide nanosheets, deionized water, ammonia, glycine, and potassium chloride was 1.3:1.8:110:1.8:1.4:0.8. A2. Titanium carbide nanosheets coated with nano-zirconia were mixed with deionized water and ethanol, and ultrasonically dispersed at 40 kHz for 20 min. The pH was adjusted to 9 by adding 1 mol / L sodium hydroxide solution, and tetraethyl orthosilicate was added. The mixture was stirred at 40 °C for 6 h, filtered, washed three times with deionized water, and dried in an oven at 60 °C for 10 min to obtain modified titanium carbide nanosheets. The mass ratio of titanium carbide nanosheets coated with nano-zirconia, deionized water, ethanol and tetraethyl orthosilicate was 2.2:50:45:1.9. A3. Modified titanium carbide nanosheets and zinc powder were mixed and stirred at 100 r / min for 1 h. After adsorption was complete, the mixture was placed in a reactor and calcined at 1050℃ for 3 h. After cooling to room temperature, the mixture was washed three times with deionized water and dried in an oven at 70℃ for 10 min to obtain composite titanium carbide nanosheets. The mass ratio of modified titanium carbide nanosheets to zinc powder was 2.8:2.2. A4. Sodium carboxymethyl cellulose was added to deionized water and stirred evenly. Composite titanium carbide nanosheets were added, and the mixture was stirred at 45°C for 13 min. After standing for 1 h, the mixture was filtered, washed three times with deionized water, and dried in an oven at 70°C for 10 min to obtain the modified material. The mass ratio of sodium carboxymethyl cellulose, deionized water, and composite titanium carbide nanosheets was 0.15:90:2.2.

[0043] Example 3 A method for preparing high-strength tungsten wire substrate diamond wire includes the following steps: S1. Tungsten powder and modified materials are mixed evenly, then cobalt hydride powder, lanthanum oxide powder, molybdenum powder, and niobium powder are added. After vacuum drying and ball milling, a composite powder is obtained. The mass ratio of tungsten powder, modified materials, cobalt hydride powder, lanthanum oxide powder, molybdenum powder, and niobium powder is 100:3:1.5:1.2:4:3. The vacuum drying temperature is 110℃, the vacuum degree is 6Pa, and the vacuum drying time is 20min. Ball milling is carried out in a ball mill. The ball material is silicon carbide ceramic grinding ball with a diameter of 10mm. The ball-to-material ratio in the ball mill is 10:1, the rotation speed is 300r / min, and the ball milling time is 15h. S2. The composite powder is pressed and sintered to obtain a sintered green body. The sintered green body is then roughened and drawn to obtain a tungsten wire substrate. The pressing pressure is 350 MPa, the pressing time is 2 min, the sintering temperature is 1600℃, the sintering time is 4 h, the diameter of the tungsten wire substrate is 55 μm, the roughing temperature is 1450℃, the deformation per pass is 25%, the roughing holding time is 20 min, and the drawing temperature is 1000℃, the holding time is 20 min. S3. Tungsten wire substrate undergoes a first nickel plating, a second sand plating, and a third nickel plating, followed by water washing and heat treatment to obtain tungsten wire substrate diamond wire. Specifically, the first nickel plating uses a 10 g / L nickel sulfate solution, resulting in a first coating thickness of 2 μm; the second sand plating uses a nickel sulfamate plating solution containing 15 g / L diamond particles with a particle size of 80 nm, resulting in a second coating thickness of 1 μm; the third nickel plating uses a 10 g / L nickel sulfate solution, resulting in a third coating thickness of 2.2 μm; the water washing involves ultrasonic cleaning at 60 kHz and 60 °C for 20 min; and the heat treatment temperature is 500 °C for 30 min.

[0044] The modified material is prepared by the following steps: A1. Zirconium oxychloride octahydrate and titanium carbide nanosheets were added to deionized water and stirred until homogeneous. Ammonia, glycine, and potassium chloride were added, and the mixture was stirred at 85°C for 10 min. The mixture was then placed in a reaction vessel and subjected to a hydrothermal reaction at 190°C for 22 h. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 80°C for 3 h to obtain titanium carbide nanosheets coated with nano-zirconium dioxide. The mass ratio of zirconium oxychloride octahydrate, titanium carbide nanosheets, deionized water, ammonia, glycine, and potassium chloride was 1.5:2:120:2:0.5:0.9. A2. Titanium carbide nanosheets coated with nano-zirconia were mixed with deionized water and ethanol, and ultrasonically dispersed at 40 kHz for 20 min. The pH was adjusted to 9 by adding 1 mol / L sodium hydroxide solution, and tetraethyl orthosilicate was added. The mixture was stirred at 40 °C for 6 h, filtered, washed three times with deionized water, and dried in an oven at 60 °C for 10 min to obtain modified titanium carbide nanosheets. The mass ratio of titanium carbide nanosheets coated with nano-zirconia, deionized water, ethanol and tetraethyl orthosilicate was 2.3:5545:2. A3. Modified titanium carbide nanosheets and zinc powder were mixed and stirred at 100 r / min for 1 h. After adsorption was complete, the mixture was placed in a reactor and calcined at 1100℃ for 4 h. After cooling to room temperature, the mixture was washed three times with deionized water and dried in an oven at 70℃ for 10 min to obtain composite titanium carbide nanosheets. The mass ratio of modified titanium carbide nanosheets to zinc powder was 3:2.3. A4. Sodium carboxymethyl cellulose was added to deionized water and stirred evenly. Composite titanium carbide nanosheets were added, and the mixture was stirred at 50°C for 15 min. After standing for 1 h, it was filtered, washed three times with deionized water, and dried in an oven at 70°C for 10 min to obtain the modified material. The mass ratio of sodium carboxymethyl cellulose, deionized water and composite titanium carbide nanosheets was 0.2:100:2.3.

[0045] Comparative Example 1 The only difference between this comparative example and Example 3 is the preparation of the modified material, as detailed below: The modified material is prepared by the following steps: A1. Titanium carbide nanosheets were mixed with deionized water and ethanol, and ultrasonically dispersed at 40 kHz for 20 min. A 1 mol / L sodium hydroxide solution was added to adjust the pH to 9. Tetraethyl orthosilicate was added, and the mixture was stirred at 40 °C for 6 h. After filtration, the mixture was washed three times with deionized water and dried in a 60 °C oven for 10 min to obtain modified titanium carbide nanosheets. The mass ratio of titanium carbide nanosheets, deionized water, ethanol, and tetraethyl orthosilicate was 2.3:55:45:2. A2. Modified titanium carbide nanosheets and zinc powder were mixed and stirred at 100 r / min for 1 h. After adsorption was complete, the mixture was placed in a reactor and calcined at 1100℃ for 4 h. After cooling to room temperature, the mixture was washed three times with deionized water and dried in an oven at 70℃ for 10 min to obtain composite titanium carbide nanosheets. The mass ratio of modified titanium carbide nanosheets to zinc powder was 3:2.3. A3. Sodium carboxymethyl cellulose was added to deionized water and stirred evenly. Composite titanium carbide nanosheets were added, and the mixture was stirred at 50°C for 15 min. After standing for 1 h, it was filtered, washed three times with deionized water, and dried in an oven at 70°C for 10 min to obtain the modified material. The mass ratio of sodium carboxymethyl cellulose, deionized water and composite titanium carbide nanosheets was 0.2:100:2.3.

[0046] Comparative Example 2 The only difference between this comparative example and Example 3 is the preparation of the modified material, as detailed below: The modified material is prepared by the following steps: A1. Zirconium oxychloride octahydrate and titanium carbide nanosheets were added to deionized water and stirred until homogeneous. Ammonia, glycine, and potassium chloride were added, and the mixture was stirred at 85°C for 10 min. The mixture was then placed in a reaction vessel and subjected to a hydrothermal reaction at 190°C for 22 h. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 80°C for 3 h to obtain titanium carbide nanosheets coated with nano-zirconium dioxide. The mass ratio of zirconium oxychloride octahydrate, titanium carbide nanosheets, deionized water, ammonia, glycine, and potassium chloride was 1.5:2:120:2:0.5:0.9. A2. Titanium carbide nanosheets coated with nano-zirconia and zinc powder were mixed and stirred at 100 r / min for 1 h. After adsorption was complete, the mixture was placed in a reactor and calcined at 1100℃ for 4 h. After cooling to room temperature, the mixture was washed three times with deionized water and dried in an oven at 70℃ for 10 min to obtain composite titanium carbide nanosheets. The mass ratio of titanium carbide nanosheets coated with nano-zirconia to zinc powder was 3:2.3. A3. Sodium carboxymethyl cellulose was added to deionized water and stirred evenly. Composite titanium carbide nanosheets were added, and the mixture was stirred at 50°C for 15 min. After standing for 1 h, it was filtered, washed three times with deionized water, and dried in an oven at 70°C for 10 min to obtain the modified material. The mass ratio of sodium carboxymethyl cellulose, deionized water and composite titanium carbide nanosheets was 0.2:100:2.3.

[0047] Comparative Example 3 The only difference between this comparative example and Example 3 is the preparation of the modified material, as detailed below: The modified material is prepared by the following steps: A1. Zirconium oxychloride octahydrate and titanium carbide nanosheets were added to deionized water and stirred until homogeneous. Ammonia, glycine, and potassium chloride were added, and the mixture was stirred at 85°C for 10 min. The mixture was then placed in a reaction vessel and subjected to a hydrothermal reaction at 190°C for 22 h. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 80°C for 3 h to obtain titanium carbide nanosheets coated with nano-zirconium dioxide. The mass ratio of zirconium oxychloride octahydrate, titanium carbide nanosheets, deionized water, ammonia, glycine, and potassium chloride was 1.5:2:120:2:0.5:0.9. A2. Titanium carbide nanosheets coated with nano-zirconia were mixed with deionized water and ethanol, and ultrasonically dispersed at 40 kHz for 20 min. The pH was adjusted to 9 by adding 1 mol / L sodium hydroxide solution, and tetraethyl orthosilicate was added. The mixture was stirred at 40 °C for 6 h, filtered, washed three times with deionized water, and dried in an oven at 60 °C for 10 min to obtain modified titanium carbide nanosheets. The mass ratio of titanium carbide nanosheets coated with nano-zirconia, deionized water, ethanol and tetraethyl orthosilicate was 2.3:55:45:2. A3. Sodium carboxymethyl cellulose was added to deionized water and stirred evenly. Modified titanium carbide nanosheets were added, and the mixture was stirred at 50°C for 15 min. After standing for 1 h, it was filtered, washed three times with deionized water, and dried in an oven at 70°C for 10 min to obtain the modified material. The mass ratio of sodium carboxymethyl cellulose, deionized water and modified titanium carbide nanosheets was 0.2:100:2.3.

[0048] Comparative Example 4 The only difference between this comparative example and Example 3 is the preparation of the modified material, as detailed below: The modified material is prepared by the following steps: A1. Zirconium oxychloride octahydrate and titanium carbide nanosheets were added to deionized water and stirred until homogeneous. Ammonia, glycine, and potassium chloride were added, and the mixture was stirred at 85°C for 10 min. The mixture was then placed in a reaction vessel and subjected to a hydrothermal reaction at 190°C for 22 h. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 80°C for 3 h to obtain titanium carbide nanosheets coated with nano-zirconium dioxide. The mass ratio of zirconium oxychloride octahydrate, titanium carbide nanosheets, deionized water, ammonia, glycine, and potassium chloride was 1.5:2:120:2:0.5:0.9. A2. Titanium carbide nanosheets coated with nano-zirconia were mixed with deionized water and ethanol, and ultrasonically dispersed at 40 kHz for 20 min. The pH was adjusted to 9 by adding 1 mol / L sodium hydroxide solution, and tetraethyl orthosilicate was added. The mixture was stirred at 40 °C for 6 h, filtered, washed three times with deionized water, and dried in an oven at 60 °C for 10 min to obtain modified titanium carbide nanosheets. The mass ratio of titanium carbide nanosheets coated with nano-zirconia, deionized water, ethanol and tetraethyl orthosilicate was 2.3:55:45:2. A3. Modified titanium carbide nanosheets and zinc powder were mixed and stirred at 100 r / min for 1 h. After adsorption was complete, the mixture was placed in a reactor and calcined at 1100℃ for 4 h. After cooling to room temperature, the mixture was washed three times with deionized water and dried in an oven at 70℃ for 10 min to obtain composite titanium carbide nanosheets. The mass ratio of modified titanium carbide nanosheets to zinc powder was 3:2.3. A4. Deionized water and composite titanium carbide nanosheets were mixed evenly, stirred at 50℃ for 15 min, allowed to stand for 1 h, filtered, washed three times with deionized water, and dried in a 70℃ oven for 10 min to obtain the modified material; the mass ratio of deionized water to composite titanium carbide nanosheets was 100.2:2.3. The performance of the tungsten wire-based diamond wires prepared in Examples 1-3 and Comparative Examples 1-4 was then tested.

[0049] Tensile strength test: The test was conducted using an electronic universal testing machine (accuracy ±0.5%). A 50mm tungsten wire substrate prepared in step S2 above was taken, with a diameter of 60μm. Both ends were fixed with special clamps and stretched at a uniform speed of 1mm / min until it broke. The tensile strength was recorded.

[0050] The elongation at break and yield strength of the tungsten wire substrate prepared in step S2 above were tested according to GB / T228.1-2021 standard.

[0051] Cutting efficiency test: Using the tungsten wire substrate diamond wire prepared in step S3 above, the material to be cut was a single-crystal silicon ingot (200mm in diameter). The cutting machine was a DS-2612 diamond wire slicer with a wire speed of 15m / s and a feed rate of 0.3mm / min. The cutting area (mm²) within 10 minutes was recorded. 2 / min).

[0052] The test results are shown in Table 1.

[0053] Table 1. Performance testing of tungsten wire-based diamond wires prepared in Examples 1-3 and Comparative Examples 1-4 As can be seen from the data in Table 1, the tungsten wire substrate diamond wire prepared using Examples 1-3 has high mechanical strength, and the tungsten wire substrate is not prone to breakage during wire drawing, and the tungsten wire substrate interface has good bonding.

[0054] Comparative Example 1: When titanium carbide nanosheets coated with nano-zirconia were replaced with modified materials prepared from titanium carbide nanosheets to prepare tungsten wire substrate diamond wire, the mechanical strength and cutting efficiency decreased. This demonstrates that the nano-zirconia formed on the surface of titanium carbide nanosheets, as a wear-resistant aggregate, can improve the wear resistance of the tungsten wire substrate and avoid the tungsten wire substrate having to withstand huge friction and compressive forces during the wire drawing process, which easily leads to wire breakage and a decrease in the strength of the tungsten wire substrate diamond wire. Furthermore, the titanium carbide nanosheets, as a carrier of nano-zirconia, can prevent the agglomeration of nano-zirconia.

[0055] Comparative Example 2 showed that the modified titanium carbide nanosheets were replaced with titanium carbide nanosheets coated with nano-zirconia. The modified material was used to prepare tungsten wire substrate diamond wire, and its mechanical strength and cutting efficiency decreased. This proves that the formation of a silica layer on the surface of titanium carbide nanosheets and the layered structure formed with the titanium carbide nanosheets can absorb and reduce the stress generated by wire drawing, avoid the wire breakage phenomenon caused by high wire drawing stress, and improve the strength of tungsten wire substrate diamond wire. Moreover, the nano-zirconia, as an intermediate layer, can slide between the titanium carbide nanosheets and the silica layer during the wire drawing process, playing the role of a rolling bearing, thereby improving the tensile properties of the tungsten wire substrate and providing high-strength diamond wire.

[0056] Comparative Example 3 showed that replacing the composite titanium carbide nanosheets with modified titanium carbide nanosheets to prepare tungsten wire-based diamond wire resulted in a decrease in mechanical strength and cutting efficiency. This demonstrated the formation of tetra-needle-shaped zinc oxide whiskers on the surface of the modified titanium carbide nanosheets. These whiskers increased the surface roughness of the modified titanium carbide nanosheets, improved their dispersibility in the tungsten wire substrate, and thus formed a denser tungsten wire substrate. Furthermore, the tetra-needle-shaped zinc oxide whiskers possessed a unique four-dimensional spatial structure, with four needle-like crystals extending radially from their core. These whiskers could mechanically interlock with the tungsten wire substrate, fixing the modified titanium carbide nanosheets within the tungsten wire substrate system and enhancing the mechanical strength of the tungsten wire substrate. In addition, the strong gripping force between the tetra-needle-shaped zinc oxide whiskers and the substrate effectively transferred the load, further enhancing the mechanical strength of the tungsten wire-based diamond wire.

[0057] Comparative Example 4 showed that the modified material prepared by replacing sodium carboxymethyl cellulose with deionized water decreased mechanical strength when used to prepare tungsten wire-based diamond wire. This demonstrates that sodium carboxymethyl cellulose coats the surface of composite titanium carbide nanosheets to form a modified material. The carboxyl groups contained in sodium carboxymethyl cellulose can be adsorbed on the surface of tungsten powder, allowing the modified material to coat the surface of tungsten powder, increasing the surface roughness of tungsten powder, increasing the contact area between tungsten powder and other metal elements, which is beneficial for synthesizing denser tungsten wire-based diamond wire and improving the mechanical strength of the tungsten wire-based diamond wire. Furthermore, during the sintering process, the carbon elements formed by the carbonization of carboxymethyl cellulose can react with the metal elements in the tungsten wire substrate raw material to form a carbide reinforcing phase, which is dispersed in the tungsten wire substrate, improving the mechanical properties of the tungsten wire-based diamond wire.

[0058] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0059] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A method for preparing high-strength tungsten wire substrate diamond wire, characterized in that, Includes the following steps: S1. Mix tungsten powder with the modified material evenly, then add cobalt hydride powder, lanthanum oxide powder, molybdenum powder, and niobium powder. After vacuum drying and ball milling, a composite powder is obtained. S2. The composite powder is pressed and sintered to obtain a sintered green body. The sintered green body is then cut and drawn to obtain a tungsten wire substrate. S3. After the tungsten wire substrate undergoes a first nickel plating, a second sand plating, and a third nickel plating, it is then washed with water and heat-treated to obtain tungsten wire substrate diamond wire. The modified material is obtained by mixing and reacting modified titanium carbide nanosheets with zinc powder, and then mixing them with sodium carboxymethyl cellulose. The modified titanium carbide nanosheets are obtained by synthesizing nano-zirconium dioxide on the surface of titanium carbide nanosheets and then coating them with a silicon dioxide nanolayer.

2. The method for preparing high-strength tungsten wire substrate diamond wire according to claim 1, characterized in that, The modified material is prepared by the following steps: A1. Add zirconium oxychloride octahydrate and titanium carbide nanosheets to deionized water, stir evenly, add ammonia, glycine and potassium chloride, stir, place in a reaction vessel, carry out hydrothermal reaction at 170-190℃ for 20-22h, cool to room temperature, filter, wash and dry to obtain titanium carbide nanosheets coated with nano-zirconia. A2. Titanium carbide nanosheets coated with nano-zirconia were mixed with deionized water and ethanol, ultrasonically dispersed, and then sodium hydroxide solution was added to adjust the pH. Tetraethyl orthosilicate was then added, and the mixture was stirred and reacted. After filtration, washing, and drying, modified titanium carbide nanosheets were obtained. A3. Mix the modified titanium carbide nanosheets and zinc powder, stir evenly, and after the adsorption is complete, place them in a reaction furnace and calcine at 1000-1100℃ for 2-4 hours. Cool to room temperature, wash and dry to obtain composite titanium carbide nanosheets. A4. Add sodium carboxymethyl cellulose to deionized water, stir evenly, add composite titanium carbide nanosheets, stir at 40-50℃ for 10-15 min, let stand, filter, wash, and dry to obtain the modified material.

3. The method for preparing high-strength tungsten wire substrate diamond wire according to claim 2, characterized in that, In step A1, the mass ratio of zirconium oxychloride octahydrate, titanium carbide nanosheets, deionized water, ammonia, glycine, and potassium chloride is (1-1.5):(1.5-2):(100-120):(1.5-2):(0.3-0.5):(0.7-0.9).

4. The method for preparing high-strength tungsten wire substrate diamond wire according to claim 2, characterized in that, In step A2, the mass ratio of the titanium carbide nanosheets coated with nano-zirconia, deionized water, ethanol and tetraethyl orthosilicate is (2-2.3):(45-55):(40-45):(1.8-2).

5. The method for preparing high-strength tungsten wire substrate diamond wire according to claim 2, characterized in that, In step A3, the mass ratio of the modified titanium carbide nanosheets to zinc powder is (2.5-3):(2-2.3).

6. The method for preparing high-strength tungsten wire substrate diamond wire according to claim 2, characterized in that, In step A4, the mass ratio of sodium carboxymethyl cellulose, deionized water and composite titanium carbide nanosheets is (0.1-0.2):(80-100):(2-2.3).

7. The method for preparing a high-strength tungsten wire substrate diamond wire according to claim 1, characterized in that, In step S1, the mass ratio of tungsten powder, modified material, cobalt hydride powder, lanthanum oxide powder, molybdenum powder, and niobium powder is 100:(2-3):(1-1.5):(1-1.2):(3-4):(2-3); In step S1, the vacuum drying temperature is 100-110℃, the vacuum degree is 4-6Pa, and the vacuum drying time is 15-20min; In step S1, the ball milling is carried out in a ball mill. The ball material is silicon carbide ceramic grinding balls with a diameter of 10 mm. The ball-to-material ratio in the ball mill is (8-10):1, the rotation speed is 200-300 r / min, and the ball milling time is 10-15 h.

8. The method for preparing high-strength tungsten wire substrate diamond wire according to claim 1, characterized in that, In step S2, the pressing pressure is 300-350 MPa, and the pressing time is 1-2 min; In step S2, the sintering temperature is 1500-1600℃ and the sintering time is 2-4h; In step S2, the diameter of the tungsten wire substrate is 40-60 μm; In step S2, the billet temperature is 1350-1450℃, the deformation per pass is 15-25%, and the billet holding time is 10-20 min. In step S2, the drawing temperature is 900-1000℃ and the holding time is 10-20min.

9. The method for preparing high-strength tungsten wire substrate diamond wire according to claim 1, characterized in that, In step S3, the first nickel plating: the plating solution is a nickel sulfate solution with a concentration of 5-10 g / L, and the thickness of the first plating layer is 1.5-2 μm; In step S3, the second sand plating: the plating solution is a nickel aminosulfonate plating solution containing 10-15 g / L of diamond particles, the particle size of the diamond particles is 50-80 nm, and the thickness of the second plating layer is 0.5-1 μm; In step S3, the third nickel plating: the plating solution is a nickel sulfate solution with a concentration of 5-10 g / L, and the thickness of the third plating layer is 1.8-2.2 μm; In step S3, the water washing specifically involves ultrasonic cleaning at 40-60 kHz and 50-60 °C for 10-20 minutes. In step S3, the heat treatment temperature is 450-500℃ and the heat treatment time is 20-30min.

10. A tungsten wire substrate diamond wire prepared by the method for preparing high-strength tungsten wire substrate diamond wire according to any one of claims 1-9.

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